Storage stable indoaniline and indophenol dye solutions, a process for producing the same and hair dye compositions containing the same

ABSTRACT

A storage stable dye solution for use in coloring hair comprises a solution in an anhydrous solvent of at least one indophenol or indoaniline dye. These storage stable dye solutions at the time of dyeing the hair are admixed with an aqueous based cosmetic carrier conventionally employed in the hair dyeing art to provide a hair dye composition which is then immediately applied to the hair using conventional procedures.

The present invention relates to storage stable dye solutions whereinthe dye is an indoaniline or an indophenol. The invention moreparticularly relates to a process for improving the storage stability ofthese dyes in a liquid medium prior to their ultimate use in an aqueousdye composition for coloring keratinic fibers and in particular livinghuman hair.

BACKGROUND OF THE INVENTION

Indoaniline and indophenol dyes are well known and are disclosed forinstance in commonly owned U.S. Pat. Nos. 4,007,747; 3,984,402;3,977,825; 3,963,764; 3,929,404; 3,929,403; 3,894,837; 3,884,625 and3,867,094. It has been observed, however, that full commercialexploitation of these dyes for coloring hair has been somewhat hinderedprincipally because these dyes when stored in aqueous systemsconventionally employed in the hair dyeing industry lack storagestability characteristics.

Storage stability is commercially of great significance because oftencompositions are stored for long periods of time, even as long as a fewyears, and often under elevated ambient temperature conditions.

Heretofore, in an effort to improve the storage stability of these dyes,it was proposed to employ them, not in the form of a previously prepareddye solution as had been done with dye compositions based on oxidationdyes, but rather in the form an anhydrous powder which was solubilizedin an appropriate carrier immediately prior to application of theresulting dye composition to the hair.

While it would appear that this procedure not only solved the storagestability problem but also provided a way to achieve reproducibledyeings, nonetheless this procedure had its disadvantages in that thepowdered dye did not dissolve as rapidly or as completely as desired oranticipated, at least in certain solvents or cosmetic vehicles. Thus theresulting dye compositions did not, at times, exhibit all the desirablecharacteristics.

In a subsequent effort to overcome these disadvantages, it was proposedto prepare these dyes in a form which was more rapidly soluble inconventional cosmetic vehicles or carriers. Thus, the dyes weretransformed into lyophilizates or spray dried particles.

However, the dyes in these forms also exhibited disadvantages in thatthe lyophilization or spray dry operations employed to produce them arecostly. Further the resulting lyophilizates and atomzates require astorage environment which is essentially humidity-proof. Moreover, rapidsolubilization of the dyes in these forms required a significant amountof the solvent.

GENERAL DESCRIPTION OF THE INVENTION

It has now been discovered that the storage stability of indoanilinesand indophenols can be improved and hence their dyeing power preserved,or at least not appreciably diminished during storage if these dyes arestored as solutions, in particular, anhydrous alcohols or monoalkylethers of ethylene glycol.

DETAILED DESCRIPTION OF THE INVENTION

Specifically, the present invention relates to a storage stable dyesolution for use in coloring hair comprising a solution in an anhydroussolvent selected from the group consisting of ethyl alcohol, isopropylalcohol, tertiobutyl alcohol, monomethyl ether of ethylene glycol,monoethyl ether of ethylene glycol, monobutyl ether of ethylene glycoland their mixtures, of at least one dye having the formula: ##STR1##

In one embodiment of the present invention, a given dye of Formula I canhave one of the sets of values for substituents A, R₉, R₁₀, R₅, R₆, R₇and R₈, tabulated below:

    ______________________________________                                        A     R.sub.9    R.sub.10      R.sub.5                                                                            R.sub.6                                                                            R.sub.7                                                                           R.sub.8                          ______________________________________                                        OH                             H    H    H   H                                OH                             Cl   H    H   H                                OH                             CH.sub.3                                                                           H    H   H                                OH                             H    Cl   H   H                                OH                             H    CH.sub.3                                                                           H   H                                 ##STR2##                                                                           H          H             H    Cl   H   H                                 ##STR3##                                                                           H          C.sub.2 H.sub.5                                                                             H    Cl   H   H                                 ##STR4##                                                                           H          CH.sub.2 CH.sub.2 OH                                                                        H    Cl   H   H                                 ##STR5##                                                                           CH.sub.2 CH.sub.2 OH                                                                     CH.sub.2 CH.sub.2 OH                                                                        H    H    H   H                                 ##STR6##                                                                           CH.sub.3   CH.sub.3      CH.sub.3                                                                           H    H   H                                 ##STR7##                                                                           C.sub.2 H.sub.5                                                                          CH.sub.2 CONH.sub.2                                                                         CH.sub.3                                                                           H    H   H                                 ##STR8##                                                                           C.sub.2 H.sub.5                                                                          (CH.sub.2).sub.2 NHSO.sub.2 CH.sub.3                                                        CH.sub.3                                                                           H    H   H                                 ##STR9##                                                                           CH.sub.3   CH.sub.3      H    Cl   H   H                                ______________________________________                                    

while, with any one of these sets of values, the dye can also have oneof the sets of values for substituents R₁, R₂, R₃ and R₄ tabulatedbelow:

    ______________________________________                                        R.sub.1   R.sub.2   R.sub.3       R.sub.4                                     ______________________________________                                        CH.sub.3  H         CH.sub.3      H                                           CH.sub.3  H         H             CH.sub.3                                    CH.sub.3  H         NH.sub.2      H                                           CH.sub.3  H         NH.sub.2      CH.sub.3                                    CH.sub.3  H         NHCOCH.sub.3  H                                           CH.sub.3  H         NHCOCH.sub.3  CH.sub.3                                    CH.sub.3  H         NHCONH.sub.2  H                                           OCH.sub.3 H         NHCOCH.sub.3  H                                           ______________________________________                                    

In another embodiment of the invention, a given dye of formula I canhave one of the sets of values for substituents A, R₉, R₁₀, R₅, R₆, R₇and R₈ tabulated below:

    ______________________________________                                        A         R.sub.9                                                                              R.sub.10                                                                              R.sub.5                                                                             R.sub.6                                                                              R.sub.7                                                                            R.sub.8                            ______________________________________                                         ##STR10##                                                                              H      H       CH.sub.3                                                                            OCH.sub.3                                                                            H    CH.sub.3                            ##STR11##                                                                              H      H       H     CH.sub.3                                                                             H    CH.sub.3                           ______________________________________                                    

while, with any one of these sets of values, the dye can also have oneof the sets of values for R₁, R₂, R₃ and R₄ tabulated below:

    ______________________________________                                        R.sub.1  R.sub.2  R.sub.3       R.sub.4                                       ______________________________________                                        CH.sub.3 H        NH.sub.2      H or CH.sub.3                                 CH.sub.3 H        NHCOCH.sub.3  CH.sub.3                                      CH.sub.3 H        NHCONH.sub.2  H                                             OCH.sub.3                                                                              H        NHCOCH.sub.3  H                                             ______________________________________                                    

In yet another embodiment of the invention, a given dye of formula I canhave one of the sets of values for substituents A, R₉, R₁₀, R₅, R₆, R₇and R₈ tabulated below:

    ______________________________________                                        A       R.sub.9                                                                              R.sub.10      R.sub.5                                                                            R.sub.6                                                                            R.sub.7                                                                            R.sub.8                           ______________________________________                                         ##STR12##                                                                            H      CH.sub.3      H    Cl   H    H                                  ##STR13##                                                                            C.sub.2 H.sub.5                                                                      CH.sub.2 CONH.sub.2                                                                         H    H    H    H                                  ##STR14##                                                                            C.sub.2 H.sub.5                                                                      (CH.sub.2).sub.2 NHSO.sub.2 CH.sub.3                                                        H    H    H    H                                 ______________________________________                                    

while, with any one of these sets of values, the dye can also have oneof the sets of values for substituents R₁, R₂, R₃ and R₄ tabulatedbelow:

    ______________________________________                                        R.sub.1   R.sub.2   R.sub.3       R.sub.4                                     ______________________________________                                        CH.sub.3  H         CH.sub.3      H                                           CH.sub.3  H         H             CH.sub.3                                    CH.sub.3  H         NH.sub.2      H                                           CH.sub.3  H         NH.sub.2      CH.sub.3                                    CH.sub.3  H         NHCOCH.sub.3  CH.sub.3                                    CH.sub.3  H         NHCONH.sub.2  H                                           OCH.sub.3 H         NHCOCH.sub.3  H                                           ______________________________________                                    

In still another embodiment of the present invention, a given dye offormula I can have one of the sets of values for substituents A, R₉,R₁₀, R₅, R₆, R₇ and R₈ tabulated below:

    ______________________________________                                        A      R.sub.9    R.sub.10      R.sub.5                                                                            R.sub.6                                                                           R.sub.7                                                                           R.sub.8                          ______________________________________                                         ##STR15##                                                                           CH.sub.2 CH.sub.2 OH                                                                     CH.sub.2 CH.sub.2 OH                                                                        H    H   H   H                                 ##STR16##                                                                           CH.sub.3   CH.sub.3      CH.sub.3                                                                           H   H   H                                 ##STR17##                                                                           CH.sub.3   CH.sub.3      H    Cl  H   H                                 ##STR18##                                                                           C.sub.2 H.sub.5                                                                          CH.sub.2 CONH.sub.2                                                                         CH.sub.3                                                                           H   H   H                                 ##STR19##                                                                           C.sub.2 H.sub.5                                                                          CH.sub.2 CONH.sub.2                                                                         H    H   H   H                                 ##STR20##                                                                           C.sub.2 H.sub.5                                                                          (CH.sub.2).sub.2 NHSO.sub.2 CH.sub.3                                                        CH.sub.3                                                                           H   H   H                                 ##STR21##                                                                           C.sub.2 H.sub.5                                                                          (CH.sub.2).sub.2 NHSO.sub.2 CH.sub.3                                                        H    H   H   H                                ______________________________________                                    

while, with any one of these sets of values, the substituents R₁, R₂, R₃and R₄ have the following meanings: R₁ is methyl, R₂ is hydrogen, R₃ is--NHCOOC₂ H₅ and R₄ is hydrogen.

These dyes can be prepared in accordance with known procedures such asthose set forth in the above enumerated U.S. patents.

As a representative example, the dyes can be prepared by condensing abase, such as a paraphenylene diamine or a para amino phenol, on acoupler such as a phenol or a meta amino phenol in an aqueous medium, ata pH equal to or greater than 8, in the presence of an oxidizing agentsuch as potassium ferricyanide, potassium persulfate or H₂ O₂.

It is also possible to prepare these dyes from a quinone iminecorresponding to the paraphenylene diamine and para amino phenol andcondensing this quonone imine on the coupler mentioned above.

Alternatively these dyes can be prepared from a nitroso derivative ofthe base, principally from tertiary paraphenylene diamines, andcondesning this para nitroso derivative on the said coupler.

The most particularly preferred compounds in accordance with the presentinvention are prepared by combining a base selected from: para-aminophenol, 3-chloro-4-amino phenol, 3-methyl-4-amino phenol,2-methyl-4-amino phenol, 2-chloro-4-amino phenol, 2,6-dimethyl-3-methoxyparaphenylene diamine, 2,5-dimethyl paraphenylene diamine, 2-chloroparaphenylene diamine, 3-methyl-4-amino N,N(ethyl, carbamylmethyl)aniline, 3-methyl-4-amino N,N-(ethyl, mesylaminoethyl) aniline, 4-aminoN,N-(ethyl, carbamylmethyl) aniline, 4-amino N,N-(ethyl,mesylaminoethyl) aniline, 4-amino N,N-(di-β-hydroxyethyl) aniline,3-chloro-4-methylamino aniline, 4-dimethylamino-2-methyl aniline,4-dimethylamino-3-chloro aniline, 3-chloro-4-ethylamino aniline,3-chloro-4-N,β-hydroxyethylamino aniline and a coupler selected from:2-methyl-5-amino phenol, 2,6-dimethyl-3-amino phenol,2,6-dimethyl-3-acetylamino phenol, 2-methyl-5-ureido phenol and2-methoxy-5-acetylamino phenol.

Other compounds includable in the definition of the present inventionand useful in the exploitation thereof are:

N-[(4'-hydroxy)phenyl]-3-acetylamino-6-methyl benzoquinone imine,

N-[(4'-hydroxy-2'-chloro)phenyl]-3-acetylamino-6-methyl benzoquinoneimine,

N-[(4'-hydroxy-2'-methyl)phenyl]-3-acetylamino-6-methyl benzoquinoneimine,

N-[(4'-hydroxy-3'-methyl)phenyl]-3-acetylamino-6-methyl benzoquinoneimine,

N-[(4'-hydroxy-3'-chloro)phenyl]-3-acetylamino-6-methyl benzoquinoneimine,

N-[(4'-amino-3'-chloro)phenyl]-3-acetylamino-6-methyl benzoquinoneimine,

N-[[4'-N,N-(ethyl,carbamylmethyl)amino-2'-methyl]phenyl]-3-acetylamino-6-methylbenzoquinone imine,

N-[[4'-N,N-(ethyl,mesylaminoethyl)amino-2'-methyl]phenyl]-3-acetylamino-6-methylbenzoquinone imine,

N-[[4'-N,N-(di-β-hydroxyethyl)amino]phenyl]-3-acetylamino-6-methylbenzoquinone imine,

N-[(4'-N,N-dimethylamino-2'-methyl)phenyl]-3-acetylamino-6-methylbenzoquinone imine,

N-[(4'-N,N-dimethylamino-3'-chloro)phenyl]-3-acetylamino-6-methylbenzoquinone imine,

N-[(4'-N-ethylamino-3'-chloro)phenyl]-3-acetylamino-6-methylbenzoquinone imine and

N-[(4'-N-β-hydroxyethylamino-3'-chloro)phenyl]-3-acetylamino-6-methylbenzoquinone imine.

Other dyes usefully employed in the composition of the present inventioninclude:

N-[[4'-N,N-(ethyl,carbamylethyl)amino]phenyl]-3-carbethoxyamino-6-methoxy benzoquinoneimine,

N-[(4'-hydroxy-2'-chloro)phenyl]-3-ureido-6-methoxy benzoquinone imine,

N-[(4'-methylamino-3'-chloro)phenyl]-3-ureido-6-methoxy benzoquinoneimine and

N-[[4'-N,N-(ethyl,carbamylmethyl)amino-3'-methyl]phenyl]-3-carbethoxyamino-6-methoxybenzoquinone imine.

The most particularly preferred storage stable dye solutions of thepresent invention are those which are solutions in ethyl alcohol,isopropyl alcohol, tertiobutyl alcohol, the monomethyl ether of ethyleneglycol, monoethyl ether of ethylene glycol and monobutyl ether ofethylene glycol, of the following dyes:

N-[(4'-amino-3'-methoxy-2',6'-dimethyl)phenyl]-2,6-dimethyl-3-acetylaminobenzoquinone imine,

N-[(4'-β-hydroxyethylamino-3'-chloro)phenyl]-6-methyl-3-ureidobenzoquinone imine,

N-[[4'-N,N(ethyl, carbamylmethyl)amino]phenyl]-6-methyl-3-carbethoxyamino benzoquinone imine,

N-[(4'-methylamino-3'-chloro)phenyl]-6-methyl-3-ureido benzoquinoneimine,

N-[(4'-methylamino-3'-chloro)phenyl]-2,6-dimethyl-3-acetylaminobenzoquinone imine,

N-[(4'-hydroxy-2'-chloro)phenyl]-2,6-dimethyl-3-acetylamino benzoquinoneimine,

N-[(4'-hydroxy-2'-chloro)phenyl]-6-methyl-3-ureido benzoquinone imine,

N-[[4'-N,N-(ethyl,carbamylmethyl)amino-2'-methyl]phenyl]-6-methyl-3-acetylaminobenzoquinone imine,

N-[[4'-N,N-(ethyl,carbamylmethyl)amino-2'-methyl]phenyl]-6-methyl-3-ureido benzoquinoneimine,

N-[[4'-N,N-(ethyl,carbamylmethyl)amino]phenyl]-2,6-dimethyl-3-acetylamino benzoquinoneimine,

N-[(4'-amino-3'-chloro)phenyl]-2,6-dimethyl-3-acetylamino benzoquinoneimine,

N-[(4'-amino-3',6'-dimethyl)phenyl]-6-methyl-3-ureido benzoquinoneimine,

N-[[4'-N,N-(ethyl, mesylamino)amino-2'-methyl]phenyl]-3-amino-6-methylbenzoquinone imine,

N-[[4'-N,N-(ethyl, mesylamino)amino]phenyl]-2,6-dimethyl-3-acetylaminobenzoquinone imine,

N-[(4'-hydroxy)phenyl]-3-acetylamino-6-methyl benzoquinone imine,

N-[(4'-amino-3'-chloro)phenyl]-3-acetylamino-6-methoxy benzoquinoneimine,

N-[(4'-hydroxy)phenyl]-3-amino-6-methyl benzoquinone imine,

N-[[4'-N,N(ethyl, carbamylmethyl)amino]phenyl]-3-carbethoxyamino-6-methoxy benzoquinone imine,

N-[(4'-hydroxy-2'-chloro)phenyl]-3-ureido-6-methoxy benzoquinone imine,

N-[(4'-hydroxy-2'-chloro)phenyl]-3-acetylamino-6-methoxy benzoquinoneimine,

N-[[4'-N,N-(ethyl, carbamylmethyl)amino]phenyl]-3-ureido-6-methylbenzoquinone imine,

N-[[4'-N,N-(ethyl, carbamylmethyl)amino]phenyl]-3-acetylamino-6-methoxybenzoquinone imine,

N-[(4'-hydroxy)phenyl]-3-acetylamino-2,6-dimethyl benzoquinone imine and

N-[[4'-N,N-(di-β-hydroxyethyl)amino]phenyl]-3-acetylamino-6-methylbenzoquinone imine.

Of these solutions, those in ethyl alcohol or in monoethyl ether ofethylene glycol are those which are more particularly preferred.

In the storage stable dye solutions of this invention, it is alsopossible to use a mixture of the above defined solvents and inassociation therewith one or more of the previously defined dyes. Thesestorage stable dye solutions can also contain other dyes conventionallyemployed in the dyeing of hair, such as azo, anthraquinone andnitrobenzene dyes as well as 2,5-diamino benzoquinones and aryl azopyridine N-oxides.

The indoaniline and/or indophenol dyes are generally present in thesestorage stable dye solutions in an amount between 0.001 and 5 weightpercent and preferably between 0.002 and 1 weight percent thereof. Theconcentration of the dye can, of course, be adjusted depending, forinstance, on the desired ultimate shade resulting from the applicationof the said solutions to the hair. It will be noted that by thusproceeding, it is possible to use dyes which are slowly or difficultlysoluble in conventionally employed cosmetic vehicles or carriers.Further this procedure permits the use of high dye concentrations.

The process of improving the storage stability characteristics of theseindoaniline and indophenol dyes, and hence preserving their dyeingpower, comprises dissolving said dye in an anhydrous solvent as definedabove, the dye being present in the above-indicated amounts.

The dyes stored in the said solvents retain their dyeing power for aperiod clearly longer than heretofore has been possible when the samedyes were stored in aqueous based hair dye compositions ready to beapplied to the hair.

In another embodiment of the present invention, a hair dye compositionfor immediate application to the hair can be prepared by admixing acosmetic vehicle conventionally employed in dyeing hair with a storagestable dye solution as defined above.

Thus, storage stable dye solutions of the present invention can beadmixed with an aqueous based cosmetic carrier or vehicle to which hasbeen added a sufficient amount of an alkalizing or acidifying agent soas to adjust the pH of the resulting hair dye composition to a valuebetween 1 and 11 and preferably between 3 and 10.

The said aqueous based hair dye compositions can also include one ormore of a solvent, a polymer, a cationic treating product, an amide, athickening agent, a surface active agent or one or more adjuvantsconventionally employed in capillary cosmetic compositions such as asolar filter, an optical bluing agent, an anti-oxidant, a sequesterantor a perfume.

These aqueous based hair dye compositions can also contain an oxidizingagent.

Representative alkalinizing agents include mono- or tri-ethanol amine,ammonia, sodium phosphate or sodium carbonate; representative acidifyingagents include phosphoric acid, hydrochloric acid, lactic acid, tartaricacid, acetic acid or citric acid. The pH adjusting agents are destinedto regulate the pH of the hair dye composition to the values indicatedabove.

Representative solvents usefully employed in the hair dye compositioninclude low molecular weight alcohols, having 1-4 carbon atoms such asethyl alcohol or isopropyl alcohol or glycols such as the monomethyl,monoethyl or monobutyl ether of ethylene glycol, propylene glycol andthe monoethyl ether of diethylene glycol. The said solvent is present inan amount between 0.5 and 50, and preferably between 1 and 15, weightpercent of the said hair dye composition.

Representative cosmetic polymers include polyvinylpyrrolidone having amolecular weight of 10,000 to 360,000; copolymers of 10% crotonic acidand 90% vinyl acetate, having a molecular weight of 10,000 to 70,000;copolymers of vinyl pyrrolidone (VP) and vinyl acetate (VA) having amolecular weight of 30,000 to 200,000, the VP/VA ratio being from 30/70to 70/30; cationic polymers such as polymers of quaternizedpolyvinylpyrrolidone, quaternized cellulose derivatives, copolymers ofN-vinylpyrrolidone and dimethylaminoethyl methacrylate and polyethyleneglycol, quaternized with dimethyl sulfate, crosslinked or not.

The cosmetic polymers or resins are employed in an amount between 0.1 to3 weight percent and preferably between 0.3 and 2 weight percent.

Representative amides include mono- or diethanolamides of fatty acids,optionally oxyethylenated.

Representative thickening agents include cellulosic derivatives such ascarboxymethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethylcellulose.

Representative surface active agents include anionic, cationic,non-ionic or amphoteric surfactants such as the sulfates, ether sulfatesand sulfonates of fatty alcohols; fatty acids or alcohols optionallyoxyethylenated; oxyethylenated alkyl phenols; amines; and quaternizedammonium salts such as trimethyl cetyl ammonium bromide and cetylpyridinium bromide.

Representative other adjuvants include benzylidene camphor, as a solarfilter; butyl hydroxy anisole; sodium bisulfite, as an antioxidizingagent; and ethylene diamine tetraacetic acid, as a complexing agent.

When employed, the oxidizing agent can be H₂ O₂ and it can be present inan amount between 1 to 6% by weight of the hair dye composition. Ureaperoxide or per salts such as ammonium persulfate can also be employedas the oxidizing agent.

The amount of the storage stable dye solution, containing the dyes ofFormula I, relative to the cosmetic vehicle such as defined above,ranges between 1 and 80% and preferably between 5 and 50%. Further, theamount can vary depending upon the concentration of the dye of Formula Iin the storage stable dye solution and on the strength or depth of theshade that is desired to be imparted to the hair. It will be noted thatit is possible to employ dye concentrations clearly higher thanpreviously possible and thus from this fact, obtain a stronger and widerrange of hair shades.

The admixture of the storage stable dye solution and the aqueous basedcosmetic vehicle can be produced in various ways using known devicessuch as those having two separated compartments, one of which containsthe storage stable dye solution of this invention, the other containingthe cosmetic vehicle.

A preferred embodiment of the present invention comprises using anaerosol device having two compartments, whereby the mixture of thesolvent phase containing the said dyes with the aqueous phaseconstituting the cosmetic vehicle is effected by means of a valve.Representative propellants for use in these aerosols include nitrogen,nitrous oxide, volatile hydrocarbons such as butane, isobutane, propaneor preferably the fluorinated hydrocarbons (sold under the name Freon),and particularly fluorochloro hydrocarbons such asdichlorodifluoromethane (Freon 12), dichlorotetrafluoromethane (Freon114) and trichloromonofluoromethane (Freon 11). These propellants can beused alone or in combination. A particularly effective propellantcombination is a mixture of Freon 114 and Freon 12 present inproportions varying from 40:60 to 80:20, respectively.

Other known devices can also be employed and include, for instance, thepackaging means described in commonly owned French Pat. Nos. 1,557,740;73 46537; 71 08902; 72 02321; and 76 05827.

Representative of these devices is a bottle provided with a tubularstopper having a slidable capsule for containing the storage stable dyesolution prior to its admixture with the cosmetic vehicle at theinterior of the bottle. Another useful device is a non-pressurizedcontainer provided with at least one distribution orifice on itsexterior cover which is made of a deformable supple material. Thisexterior cover which has an elongated form encloses at least one sealedand breakable rigid tube. The cosmetic vehicle is confined in the spacedefined by the exterior of this breakable rigid tube and at the interiorof the flexible cover while the storage stable dye solution of thepresent invention is confined within the breakable rigid tube.

Another example of means usefully employed with the present inventionconsists of a bottle within which is confined the cosmetic vehicle orcarrier, the bottle having disposed at the interior of the neck thereofa lid covered container or jar fitted with the storage stable dyesolution. The admixture of these components is effected in this instanceby sliding a trocar, supportingly maintained by a flange at the extremeedge of the neck of the bottle, whereby the trocar perforates the lidand the bottom of the container.

The hair dye compositions, thus prepared, are then applied to the hairin accordance with such conventional procedures as rinsing orshampooing. Conveniently, the thus applied composition is permitted toremain in contact with the hair for a period of time ranging from about3 to 30 minutes.

The use of the storage stable dye solution of the present invention inthese or similar compartmented packages or containers provides numerouseconomic advantages. Further, the production of hair dye compositionscontaining these storage stable dye solutions and the implementation ofprocedures utilizing the same are clearly less onerous than previouslyemployed compositions and procedures.

The following non-limiting examples are given to illustrate the presentinvention. Unless otherwise specified, all parts and percentages are byweight.

Examples of Cosmetic Vehicles or Carriers

The following examples illustrate various conventional cosmetic vehiclesor carriers employed in hair dyeing operations. These cosmetic carriersare used in combination with the storage stable dye solutions of thepresent invention to provide a hair dye composition which is applied,immediately after its preparation, to the hair. Obviously conventionalcosmetic carriers, other than those specifically set forth below, willoccur to those skilled in this art and thus the present invention is notto be limited either by these specifically exemplified carriers or bythe specific procedures employed in dyeing the hair.

Cosmetic Carrier A

Polyvinylpyrrolidone, M.W. 40,000--0.5 g

Trimethylcetylammonium bromide--0.2 g

Ethyl alcohol, sufficient for 12°5

Triethanolamine, sufficient for pH=7

Water, sufficient for--100 cc

Cosmetic Carrier B

Polyvinylpyrrolidone, M.W. 40,000--0.5 g

Trimethylcetylammonium bromide--0.2 g

GAFQUAT 734, in active material--0.4 g

Ethyl alcohol, sufficient for 37°5

Triethanolamine, sufficient for pH=7

Water, sufficient for--100 cc

Cosmetic Carrier C

Copolymer of vinyl acetate/crotonic acid (90/10), M.W.45,000-50,000--2.0 g

Copolymer of vinyl acetate/vinylpyrrolidone, (40/60), sold under thename PVP/VA S630--0.38 g

Ethyl alcohol, sufficient for 37°5

Triethanolamine, sufficient for pH=7

Water, sufficient for--100 cc

Cosmetic Carrier D

Polyvinylpyrrolidone, M.W. 40,000--0.8 g

Trimethylcetylammonium bromide--0.2 g

Triethanolamine, sufficient for pH=7

Water, sufficient for--100 cc

Cosmetic Carrier E

Trimethylcetylammonium bromide--0.125 g

Copolymer of vinylpyrrolidone/vinyl acetate (60/40), sold under the nameof PVP/VA S630--0.60 g

H₂ O₂ (200 vol.) sufficient for--12.5 vol.

Orthophosphoric acid, sufficient for pH=3

Ethyl alcohol, sufficient for 37°5

Water, sufficient for--100 cc

Cosmetic Carrier F

Copolymer of vinylpyrrolidone/vinyl acetate, (70/30), M.W. 40,000--0.35g

Trimethylcetylammonium bromide--0.1 g

Ethyl alcohol, sufficient for 33°

Triethanolamine, sufficient for pH=7

Water, sufficient for--100 cc

Cosmetic Carrier G

Copolymer of vinylpyrrolidone/vinyl acetate (60/40), sold under the nameof PVP/VA S630--0.25 g

Monoethanolamine, sufficient for pH=9

Water, sufficient for--100 cc

Cosmetic Carrier H

Sodium lauryl ether sulfate (30% active material) sold under the markDelf 8533--25.0 g

Butyl cellosolve--1.0 g

Copradiethanolamide--5.0 g

Citric acid, sufficient for pH=6

Water, sufficient for--100 cc

Cosmetic Carrier I

Trimethylcetylammonium bromide--5.0 g

Lauryl alcohol oxyethylenated with 12.5 moles of ethylene oxide soldunder the mark FREPAL 12--4.0 g

Citric acid, sufficient for pH=4

Water, sufficient for--100 cc

It will be noted that in cosmetic carriers A and C, the ethyl alcoholcan be replaced by isopropyl alcohol in those instances where thestorage stable dye solution contains isopropyl alcohol.

GAFQUAT 734 used in cosmetic carrier B is quaternary copolymer ofpolyvinylpyrrolidone having an average molecular weight lower than100,000 and is provided in the form of a 50% solution in alcohol havinga relative viscosity, Ostwald-Fenske, of 2.5-3.5.

Examples of Storage Stable Dye Solutions and Hair Dye CompositionsPrepared Therefrom

Table I below illustrates various storage stable dye solutions of thepresent invention. This Table contains information and data relating tothe nature of the dyes employed, the amount in grams of each dye used,the nature of the solvent employed in preparing these solutions and theamount of solvent used.

Example 1

(a) After eight months of storage in a tight container, dye solution S₁set forth in Table I is used to prepare a hair dye composition by mixing5 cc of this storage stable solution at the moment of use with 20 cc ofcosmetic carrier A defined above.

The resulting hair dye composition is applied to light chestnut coloredhair. The hair, after drying, untangles easily and exhibits particularlyluminous mahogany glints.

(b) After 4 months of storage in an ampoule, dye solution S₁, as definedin Table I, is released by breaking the ampoule and 5 cc of this storagestable solution are mixed with 20 cc of cosmetic carrier C. Theresulting hair dye composition in the form of a hair setting lotion isthen applied to blonde hair using conventional procedures. This hairsetting lotion imparts to the hair particularly esthetic light copperymahogany glints.

(c) By replacing, in the preceding example, cosmetic carrier C withcosmetic carrier E, and by using the same amount of the storage stabledye solution and carrier, and by applying the resulting hair dyecomposition by washing natural blonde hair, there is obtained, afterdrying, slightly brightened hair which is easily untangled and whichexhibits very luminous mahogany glints.

(d) At the moment of use, 2.5 cc of solution S₁ previously stored for 2months, is mixed with 22.5 cc of cosmetic carrier G. The resulting hairsetting lotion is then applied to deep blonde hair, which after drying,exhibits particularly esthetic mahogany glints.

Examples 2-25

Table II below illustrates the use of the storage stable dye solutionsdefined in Table I, in the preparation of various types of hair dyecompositions. Table II includes data relating to the nature of thestorage stable dye solution employed, the duration of storage, theamount of the dye solution mixed with the selected cosmetic vehicle, theselected cosmetic vehicle and the amount thereof employed in admixturewith the storage stable dye solution, the pH of the hair dye compositionresulting from this admixture, the nature of the hair being dyed and theshade or coloration obtained. The mixture of the storage stable dyesolution with the cosmetic carrier can be effected in accordance withconventional procedures, including those mentioned in Example 1.Additional means of effecting this admixture are described in commonlyowned French Pat. Nos. 1,557,740; 73 46537; 71 08902; 72 02321; and 7605827.

In carrying out the present invention, the hair dye compositionsprepared with cosmetic carriers A, B, C, D, E, F and G are applied by arinsing technique while the hair dye compositions prepared with cosmeticcarriers H and I are applied as a shampoo.

Example 26

A hair dye composition is prepared using an aerosol container having twoseparated compartments. One of the compartments contains a storagestable dye solution of this invention; the other contains a conventionalcosmetic carrier. These two solutions provide at the moment of use a 1:1mixture thereof. The storage stable dye solution is solution S₉, setforth in Table I, while the cosmetic carrier employed is carrier Ddefined above. The storage stable dye solution and carrier are eachpresent in an amount of 42.5 cc. 15 g of an aerosol propellantcomprising a mixture of Freon 11 and Freon 12 in a weight ratio of 60/40are admixed with the storage stable dye solution.

20 g of this hair dye composition are applied, using a rinsingtechnique, to hair having a light chestnut coloration. After drying, thehair untangles easily and exhibits particularly luminous mahoganyglints.

Example 27

A hair dye composition is prepared using an aerosol container having twoseparated compartments, one of the compartments contains a storagestable dye solution of this invention, the other contains a conventionalcosmetic carrier. These two solutions provide at the moment of use a 1:1mixture thereof. The storage stable dye solution is solution S₁₀, setforth in Table I, while the cosmetic carrier is carrier D, definedabove. Dye solution S₁₀ and carrier D are each present in an amount of42.5 cc. 15 g of an aerosol propellant comprising a mixture of Freon 114and Freon 12, in a weight ratio of 80/20, are mixed with the storagestable dye solution.

20 g of this hair dye composition using a conventional rinsing techniqueare applied to hair having a deep blonde coloration. After drying, thehair untangles easily and exhibits a beautiful, irridescent, deep blondeshade.

                                      TABLE I                                     __________________________________________________________________________                              Amount                Amount                        Solution                                                                            Dyes                (g)   Solvents        (cc)                          __________________________________________________________________________    S.sub.1                                                                             N-[(4'-hydroxy-2'-chloro)phenyl]                                              3-acetylamino-2,6-dimethyl                                                    benzoquinone imine  0.660 Absolute ethyl alcohol                                                                        sufficient for                                                                100                                 N-[(4'-hydroxy-2'-chloro)phenyl]-3-                                           ureido-6-methyl benzoquinone imine                                                                0.130                                                     N-[[4'-N,N(ethyl, carbamylmethyl)                                             amino-2'-methyl]phenyl] 3-acetyl-                                             amino-6-methyl benzoquinone imine                                                                 0.018                                               S.sub.2                                                                             N-[(4'-hydroxy-2'-chloro)phenyl]                                              3-acetylamino-2,6-dimethyl benzo-                                             quinone imine       0.017                                                     N-[(4'-hydroxy)phenyl]-2,6-dimethyl                                           3-acetylamino benzoquinone imine                                                                  0.005                                                     N-[(4'-hydroxy-2'-chloro)phenyl]                                              3-ureido-6 methyl benzoquinone imine                                                              0.002                                                     N-[[4'-N,N(ethyl, mesylaminoethyl)                                                                      Absolute ethyl alcohol                                                                        sufficient for                      amino-2'-methyl]phenyl] 3-amino-6         100                                 methyl benzoquinone imine                                                                         0.066                                                     2-N-β-hydroxyethylamino-5-(4-di-β-                                  hydroxy ethylamino anilino)-1,4-                                              benzoquinone        0.002                                               S.sub.3                                                                             N-[(4'-hydroxy-2'-chloro)phenyl]                                              3-acetylamino-2,6-dimethyl benzo-                                             quinone imine       0.090                                                     N-[(4'-hydroxy-2'-chloro)phenyl]                                              3-acetylamino-6-methoxy benzo-                                                quinone imine       0.008                                                     N-[[4'-N,N(ethyl, carbamylmethyl)                                                                       Absolute ethyl alcohol                                                                        sufficient for                      amino-2'-methyl]phenyl] 3-acetyl-         100                                 amino-6-methyl benzoquinone imine                                                                 0.015                                                     2-N-β-hydroxyethylamino-5-(4-di-β-                                  hydroxy ethylamino anilino)-1,4-                                              benzoquinone        0.006                                               S.sub.4                                                                             N-[(4'-hydroxy-2'-chloro)phenyl]                                              3-acetylamino-2,6-dimethyl benzo-                                             quinone imine       0.115                                                     N-[(4'-hydroxy)phenyl]-2,6-dimethyl-                                          3-acetylamino benzoquinone imine                                                                  0.085                                                     N-[(4'-hydroxy-2'-chloro)phenyl]                                                                        Absolute ethyl alcohol                                                                        sufficient for                      3-ureido-6 methoxy benzoquinone           100                                 imine               0.360                                               S.sub.5                                                                             N-[(4'-hydroxy-2'-chloro)phenyl]                                              3-acetylamino-2,6-dimethyl benzo-                                             quinone imine       0.148                                                     N-[(4'-hydroxy-2'-chloro)phenyl]-3-                                           ureido-6 methyl benzoquinone imine                                                                0.005                                               N-[[4'N,N(ethyl, carbamylmethyl)                                                    amino-2'-methyl]phenyl]-3-acetyl-                                                                       Absolute ethyl alcohol                                                                        sufficient for                      amino-6 methyl benzoquinone imine                                                                 0.020                 100                                 2-N-β-hydroxyethylamino-5-(4-di-β-                                  hydroxyethylamino anilino) 1,4-                                               benzoquinone        0.002                                               S.sub.6                                                                             N-[4'-hydroxy-2'-chloro)phenyl]                                               3-ureido-6 methyl benzoquinone imine                                                              0.060                                               N-[[4'-N,N(ethyl, mesylaminoethyl)                                                                      Absolute ethyl alcohol                                                              sufficient for                                      amino-2'-methyl]phenyl] 3-amino-6-        100                                 methyl benzoquinone imine                                                                         0.119                 100                           S.sub.7                                                                             N-[(4'-hydroxy-2'-chloro)phenyl]-                                             3-acetylamino-2,6-dimethyl benzo-                                             quinone imine       0.600                                                     N-[(4'-hydroxy-2'-chloro)phenyl]-                                             3-ureido-6-methyl benzoquinone imine                                                              0.012                                                     N-[[4'-N,N(ethyl, carbamylmethyl)                                             amino-2'-methyl-2]phenyl]-3-acetyl-                                                                     Absolute ethyl alcohol                                                                        sufficient for                      amino-6-methyl-6 benzoquinone             100                                 imine               0.012                                                     2-N-β-hydroxyethylamino-5-(4-di-β-                                  hydroxy ethylamino- anilino)-1,4-                                             benzoquinone        0.008                                               S.sub.8                                                                             N-[(4'-hydroxy-2'-chloro)phenyl]-                                             3-ureido-6-methyl benzoquinone imine                                                              0.120                                                     N-[[4'-N,N-(ethyl, mesylaminoethyl)                                           amino-2'-methyl]phenyl]-3-amino-3-                                                                      Absolute ethyl alcohol                                                                        sufficient for                      methyl benzoquinone imine                                                                         0.238                 100                           S.sub.9                                                                             N-[(4'-hydroxy-2-'-chloro)phenyl]-                                            3-acetylamino-2,6-dimethyl benzo-                                             quinone imine       0.660                                                     N-[(4'-hydroxy-2'-chloro)phenyl]-                                             3-ureido-6-methyl benzoquinone imine                                                              0.130                                                     N-[[4'-N,N-(ethyl, carbamylmethyl)                                                                      Absolute ethyl alcohol                                                                        sufficient for                      amino-2'-methyl]phenyl]-3-acetyl-         100                                 amino-6-methyl benzoquinone imine                                                                 0.018                                                     N-[[4'-N,N-(ethyl, carbamylmethyl)                                            amino]phenyl]-3-carbethoxyamino-6-                                            methoxy benzoquinone imine                                                                        0.010                                               S.sub.10                                                                            N-[(4'-hydroxy-2'-chloro)phenyl]-                                             3-acetylamino-2,6-dimethyl benzo-                                             quinone imine       0.148                                                     N-[(4'-hydroxy-2'-chloro)phenyl]-                                             3-ureido-6-methyl benzoquinone imine                                                              0.005                                                     N-[[4'-N,N-(ethyl, carbamylmethyl)                                                                      Absolute ethyl alcohol                                                                        sufficient for                                                                100                                 N-[[4'-N,N-(ethyl, carbamylmethyl)                                            amino-2'-methyl]phenyl]-3-acetyl-                                             amino-6-methyl benzoquinone imine                                                                 0.002                                                     2-N-β-hydroxyethylamino-5-(4-di-β-                                  hydroxyethylamino anilino)-1,4-                                               benzoquinone        0.002                                               S.sub.11                                                                            N-[(4'-hydroxy)phenyl]-2,6-                                                   dimethyl-3-acetylamino benzo-                                                 quinone imine       0.820                                                     N-[(4'-hydroxy-2'-chloro)phenyl]-                                             3-ureido-6-methyl benzoquinone imine                                                              0.220                                                     N-[(4'-amino)phenyl]-2,6-dimethyl-                                                                      Monoethyl ether of ethylene                                                                   sufficient for                      3-acetylamino benzoquinone imine                                                                  0.064 glycol          100                                 2-N-β-hydroxyethylamino-5-(2-                                            methoxy-4-amino anilino)-1,4-benzo-                                           quinone             0.088                                               S.sub.12                                                                            N-[(4'-amino)phenyl]-2,6-dimethyl-                                            3-acetylamino benzoquinone imine                                                                  0.238                                                     N-[(4'-hydroxy-2'-chloro)phenyl]-                                             3-ureido-6-methyl benzoquinone imine                                                              0.006                                                     N-[(4'-hydroxy-2'-chloro)phenyl]-                                                                       Monoethyl ether of ethylene                                                                   sufficient for                      3-acetylamino-2,6-dimethyl benzo-                                                                       glycol          100                                 quinone imine       0.007                                                     2-N-β-hydroxyethylamino-5 (2-methoxy-                                    4-amino anilino)-1,4-benzoquinone                                                                 0.120                                               S.sub.13                                                                            N-[4'-amino-2'-methoxy-3',5'-                                                 dimethyl)phenyl]-3-acetylamino-                                               6-methyl benzoquinone imine                                                                       0.190                                                     N[4'-amino)phenyl]-2,6-dimethyl-                                                                        Monoethyl ether of                                                                            sufficient for                      3-acetylamino benzoquinone imine                                                                  0.105 ethylene glycol 100                                 N-[4'-hydroxy)phenyl]-3-acetyl-                                               amino-6-methyl benzoquinone imine                                                                 0.013                                               S.sub.14                                                                            N-[(4'-hydroxy)phenyl]-3-amino-                                               6-methyl benzoquinone imine                                                                       0.35                                                      N-[(4'-hydroxy-2'-chloro)phenyl]-                                             2,6-dimethyl benzoquinone imine                                                                   0.35                                                      2-N-β-hydroxyethylamino-5-(2-                                                                      Monoethyl ether of                                                                            sufficient for                      methoxy-4-amino-5-methyl anilino)-                                                                      ethylene glycol 100                                 1,4-benzoquinone    0.30                                                S.sub.15                                                                            N-[(4'-methylamino-3'-chloro)                                                 phenyl]-3-acetylamino-2,6-                sufficient for                      dimethyl benzoquinone imine                                                                       0.040 Ethyl alcohol   100                           S.sub.16                                                                            N-[(4'-hydroxy-2'-chloro)phenyl]-                                             3-acetylamino-2,6-dimethyl benzo-                                             quinone imine       0.40                                                      N-[(4'-hydroxy-2'-methyl)phenyl]-                                             3-amino-2,6-dimethyl benzoquinone                                             imine               0.10                                                      N-[[4'-N,N(ethyl, carbamylmethyl)                                                                       Ethyl alcohol   sufficient for                      amino]phenyl]-3-amino-2,6-dimethyl        100                                 benzoquinone imine  0.05                                                      N-[(4'-amino-2',5'-dimethyl)phenyl]-                                          3-ureido-6-methyl benzoquinone imine                                                              0.02                                                      N-[(4'-amino-3'-chloro)phenyl]-3-                                             acetylamino-2,6-dimethyl benzo-                                               quinone imine       0.001                                               S.sub.17                                                                            N-[[4'-N,N(ethyl, mesylaminoethyl)                                            amino-2'-methyl]phenyl]-2,5-                                                  dimethyl benzoquinone imine                                                                       0.075                                                     N-[(4'-hydroxy-2'-chloro)phenyl]-                                             3-acetylamino-2,6-dimethyl benzo-                                             quinone imine       0.10                                                      N-[(4'-ethylamino-3'-chloro)                                                                            Isopropyl alcohol                                                                             sufficient for                      phenyl]-3-acetylamino-6-methyl            100                                 benzoquinone imine  0.05                                                      2-N-β-hydroxyethylamino-5 (4-di-                                         β-hydroxyethylamino anilino)-                                            1,4-benzoquinone    0.030                                               S.sub.18                                                                            N-[(4'-hydroxy-2'-chloro)phenyl]-                                             3-acetylamino-2,6-dimethyl benzo-                                             quinone imine       0.25                                                      N-[(4'-hydroxy-2'-chloro)phenyl]-                                                                       Isopropyl alcohol                                                                             sufficient for                      2-methyl-5-ureido benzoquinone imine                                                              0.10                  100                                 N-[(4'-amino-2',6'-dimethyl-3'-                                               methoxy)phenyl]-3-acetylamino-2,6-                                            dimethyl benzoquinone imine                                                                       0.03                                                S.sub.19                                                                            N-[(4'-methylamino-3'-chloro)                                                 phenyl]-3-ureido-6-methyl benzo-                                              quinone imine       0.10                                                      N-[(4'-dimethylamino-3'-chloro)                                               phenyl]-3-amino-6-methyl benzo-                                                                         Tert. butyl alcohol                                                                           sufficient for                      quinone imine       0.005                 100                                 N-[[4'-N,N(ethyl, carbamylmethyl)                                             amino-2'-methyl]phenyl]-3-ureido-                                             6-methyl benzoquinone imine                                                                       0.01                                                S.sub.20                                                                            N-[(4'-amino-2',6'-dimethyl-3'-                                               methoxy)phenyl]-3-amino-6-methyl                                              benzoquinone imine  0.10                                                      N-[[4'-N,N(ethyl, carbamylmethyl)                                                                       Monomethyl ether of                                                                           sufficient for                      amino]phenyl]-3-acetylamino-2,6-                                                                        ethylene glycol 100                                 dimethyl benzoquinone imine                                                                       0.20                                                      N-[(4'-hydroxy-3'-methyl)phenyl]-                                             3-amino-6-methyl benzoquinone imine                                                               0.01                                                      4'-phenylamino-1':2 benzene azo-3-                                            methyl pyridine N-oxide                                                                           0.01                                                S.sub.21                                                                            N-[[4'-N,N(ethyl, carbamylmethyl)                                             amino]phenyl]-3-ureido-6-methyl                                               benzoquinone imine  0.10                                                      N-[[4'-N,N(ethyl, carbamylmethyl)                                             amino]phenyl]-3-carbethoxyamino-6-                                            methyl-benzoquinone imine                                                                         0.15                                                      N-[(4'-hydroxy-2'-chloro)phenyl]-                                                                       Monomethyl ether of                                                                           sufficient for                      3-acetylamino-2,6-dimethyl benzo-                                                                       ethylene glycol 100                                 quinone imine       0.01                                                      4'-dimethylamino-1':2 benzene azo-                                            3-methyl pyridine N-oxide                                                                         0.01                                                      2-N-β-hydroxyethylamino-5 (4-di-β-                                  hydroxyethylamino anilino)-1,4-                                               benzoquinone        0.15                                                S.sub.22                                                                            N-[(4'-di-β-hydroxyethylamino)                                           phenyl]-3-acetylamino-6-methyl                                                benzoquinone imine  0.02                                                      N-[(4'-dimethylamino-2'-methyl)                                                                         Monobutyl ether of                                                                            sufficient for                      phenyl]-3-acetylamino-6-methyl                                                                          ethylene glycol 100                                 benzoquinone imine  0.01                                                      N-[(4'-hydroxy-2'-chloro)phenyl]-                                             3-acetylamino-2,6-dimethyl benzo-                                             quinone imine       0.50                                                      N[(4'-dimethylamino-3'-chloro)                                                phenyl]-3-amino-6-methyl                                                      benzoquinone imine  0.15                                                S.sub.23                                                                            N-[[4'-N,N(ethyl, mesylaminoethyl)                                            amino]phenyl]-3-acetylamino-2,6-                                              dimethyl benzoquinone imine                                                                       0.15                                                      N-[[4'-N,N(ethyl, carbamylethyl)                                                                        Monobutyl ether of                                                                            sufficient for                      amino-2'-methyl]phenyl]-3-ureido-                                                                       ethylene glycol 100                                 6-methyl-6 benzoquinone imine                                                                     0.05                                                      N-[(4'-hydroxy-2'-chloro)phenyl]-                                             3-acetylamino-2,6-dimethyl benzo-                                             quinone imine       0.01                                                S.sub.24                                                                            N-[(4'-hydroxy-2'-chloro)phenyl]-                                                                       Monomethyl ether of                                                                           sufficient for                      3-acetylamino-2,6-dimethyl benzo-                                                                       ethylene glycol 100                                 quinone imine       3.00                                                S.sub.25                                                                            N-[[4'-N,N(ethyl, carbamylmethyl)                                                                       Monomethyl ether of                                                                           sufficient for                      amino]phenyl]-2,6-dimethyl benzo-                                                                       ethylene glycol 100                                 quinone imine       1.00                                                S.sub.26                                                                            N-[(4'-hydroxy-2'-chloro)phenyl]-                                             3-acetylamino-2,6-dimethyl benzo-                                             quinone imine       0.135                                                     N-[(4'-hydroxy)phenyl]-2,6-dimethyl                                           3-acetylamino benzoquinone imine                                                                  0.450                                                     N-[(4'-hydroxy-2'-chloro)phenyl]                                                                        Absolute ethyl alcohol                                                                        sufficient for                      6-methyl-3-ureido benzoquinone imine                                                              0.400                 100                                 N-[[4'-N,N-(ethyl, mesylaminoethyl)                                           amino]phenyl]-3-acetylamino-2,6-                                              dimethyl benzoquinone imine                                                                       0.100                                                     2-N-β-hydroxyethylamino-5-(4-ethyl,                                      β-acetylaminoethyl anilino)-1,4-                                         benzoquinone        0.430                                               S.sub.27                                                                            N-[(4'-hydroxy-3'-chloro)phenyl]-                                             3-acetylamino-6-methoxy benzo-                                                quinone imine       0.05  Monoethyl ether of                                                                            sufficient for                                                ethylene glycol 100                                 N-[(4'-β-hydroxyethylamino-3'-                                           chloro)phenyl]-3-ureido-6-methyl                                              benzoquinone imine  0.1                                                       N-[(4'-hydroxy-2'-chloro)phenyl]-                                             3-acetylamino-2,6-dimethyl benzo-                                             quinone imine       0.3                                                       N-[(4'-hydroxy-2'-chloro)phenyl]-                                             3-ureido-6-methyl benzoquinone                                                imine               0.1                                                 __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________    Solution                Cosmetic Vehicle                                                 Duration of                                                                          Amount     Amount                                                                              pH     Nature of Hair                                                                        Color of Hair               Examples                                                                            Nature                                                                             Storage                                                                              (cc)  Nature                                                                             (cc)  Composition                                                                          Being Dyed                                                                            After                       __________________________________________________________________________                                                      Treatment                   E.sub.2                                                                             S.sub.2                                                                            12 months                                                                            5     A    20    7      light blonde                                                                           light ash blonde                 S.sub.2                                                                            4 months                                                                             5     E    20    3      light blonde                                                                           light ash blonde           E.sub.3                                                                             S.sub.3                                                                            15 months                                                                            5     A    20    7      bleached beige                      E.sub.4                                                                             S.sub.4                                                                            4 months                                                                             5     B    20    7      deep blonde                                                                            light coppery                                                                 mahogany glints            E.sub.5                                                                             S.sub.5                                                                            1 month                                                                              5     B    20    7      very light                                                                             very luminous and                                                    blonde   very light                                                                    irridescent blonde               S.sub.5                                                                            1 month                                                                              5     C    20    7      very light                                                                             very luminous and                                                    blonde   very light                                                                    irridescent blonde               S.sub.5                                                                            1 month                                                                              10    D    10    7      deep blonde                                                                            irridescent deep                                                              blonde                     E.sub.6                                                                             S.sub.6                                                                            5 months                                                                             10    D    10    7      deep blonde                                                                            deep ash blonde                  S.sub.6                                                                            5 months                                                                             2.5   G    22.5  9      blonde   very luminous                                                                 ash blonde                 E.sub.7                                                                             S.sub.7                                                                            10 months                                                                            1     G    19    9      very light                                                                             very luminous                                                        blonde   pink glints                E.sub.8                                                                             S.sub.8                                                                            24 months                                                                            1     G    19    9      deep blonde                                                                            deep ash blonde            E.sub.9                                                                             S.sub.11                                                                           6 months                                                                             2.5   F    22.5  7      light chestnut                                                                         coppery mahogany                                                              light chestnut             E.sub.10                                                                            S.sub.12                                                                           17 months                                                                            2.5   F    22.5  7      blonde   very luminous                                                                 ash blonde                 E.sub.11                                                                            S.sub.13                                                                           8 days 2.5   B    22.5  7      80% white                                                                              beautiful light                                                               gray glints                E.sub.12                                                                            S.sub.14                                                                           3 months                                                                             2.5   F    22.5  7      light blonde                                                                           light golden                                                                  blonde                     E.sub.13                                                                            S.sub.15                                                                           14 months                                                                            2.5   F    22.5  7      very light                                                                             very luminous, very                                                  blonde   light ash blonde           E.sub.14                                                                            S.sub.16                                                                           9 months                                                                             5     A    20    7      light chestnut                                                                         very luminous                                                                 mahogany glints                  S.sub.16                                                                           9 months                                                                             5     C    20    7      blonde   mahogany glints            E.sub.15                                                                            S.sub.17                                                                           1 month                                                                              5     A    20    7      deep blonde                                                                            deep ash blonde                  S.sub.17                                                                           1 month                                                                              5     C    20    7      light blonde                                                                           very luminous                                                                 ashen glints               E.sub.16                                                                            S.sub.18                                                                           15 months                                                                            5     A    20    7      light blonde                                                                           coppery mahogany                                                              glints                           S.sub.18                                                                           15 months                                                                            5     C    20    7      very light                                                                             very luminous                                                        blonde   pink glints                E.sub.17                                                                            S.sub.19                                                                           9 months                                                                             5     A    20    7      natural blonde                                                                         very luminous                                                                 violet glints                    S.sub.19                                                                           9 months                                                                             5     C    20    7      blonde   irridescent blonde         E.sub.18                                                                            S.sub.20                                                                           4 months                                                                             2.5   F    22.5  7      light blonde                                                                           light ash blonde                 S.sub.20                                                                           4 months                                                                             2.5   G    22.5  9      deep blonde                                                                            irridescent ashen                                                             glints                     E.sub.19                                                                            S.sub.21                                                                           12 months                                                                            2.5   F    22.5  7      blonde   ash blonde                       S.sub.21                                                                           12 months                                                                            2.5   G    22.5  9      gray     bluish gray                E.sub.20                                                                            S.sub.22                                                                           17 months                                                                            2.5   F    22.5  7      light blonde                                                                           pink glints                      S.sub.22                                                                           17 months                                                                            2.5   G    22.5  9      chestnut mahogany glints            E.sub.21                                                                            S.sub.23                                                                           6 months                                                                             2.5   F    22.5  7      deep blonde                                                                            ashen glints                     S.sub.23                                                                           6 months                                                                             2.5   G    22.5  9      natural blonde                                                                         beautiful ashen                                                               glints                     E.sub.22                                                                            S.sub.24                                                                           10 months                                                                            1     H    19    6      bleached very luminous                                                                 pearly glints              E.sub.23                                                                            S.sub.25                                                                           20 months                                                                            1     I    19    4      very light                                                                             ashen glints                                                         blonde   (after contact                                                                time of 15 min.)           E.sub.24                                                                            S.sub.26                                                                           12 months                                                                            2.5   H    22.5  7      bleached beige (after                                                                  contact time of                                                               15 min.)                   E.sub.25                                                                            S.sub.27                                                                           13 months                                                                            2.5   F    22.5  7      light blonde                                                                           very luminous                                                                 pearly light                                                                  blonde                     __________________________________________________________________________

What is claimed is:
 1. A process for improving the storage stability ofa dye having the formula: ##STR22## and selected from the groupconsisting of (1) a dye wherein A is selected from the group consistingof hydroxy and ##STR23## R₁, R₂, R₃ and R₄ are selected from thefollowing groups of values:(a) R₁ is methyl, R₂ is hydrogen, R₃ ismethyl and R₄ is hydrogen, (b) R₁ is methyl, R₂ is hydrogen, R₃ ishydrogen and R₄ is methyl, (c) R₁ is methyl, R₂ is hydrogen, R₃ is aminoand R₄ is hydrogen, (d) R₁ is methyl, R₂ is hydrogen, R₃ is amino and R₄is methyl, (e) R₁ is methyl, R₂ is hydrogen, R₃ is acetylamino and R₄ ishydrogen, (f) R₁ is methyl, R₂ is hydrogen, R₃ is acetylamino and R₄ ismethyl, (g) R₁ is methyl, R₂ is hydrogen, R₃ is carbamylamino and R₄ ishydrogen, and (h) R₁ is methoxy, R₂ is hydrogen, R₃ is acetylamino andR₄ is hydrogen; with the proviso that when A is hydroxy, R₅, R₆, R₇ andR₈ are selected from the following groups of values: (i) R₅, R₆, R₇ andR₈ are each hydrogen, (j) R₅ is chlorine and R₆, R₇ and R₈ are eachhydrogen, (k) R₅ is methyl and R₆, R₇ and R₈ are each hydrogen, (l) R₅is hydrogen, R₆ is chlorine and R₇ and R₈ are each hydrogen, and (m) R₅is hydrogen, R₆ is methyl and R₇ and R₈ are each hydrogen; and that whenA is ##STR24## R₅, R₆, R₇, R₈, R₉ and R₁₀ are selected from thefollowing group of values: (n) R₅ is hydrogen, R₆ is chlorine and R₇,R₈, R₉ and R₁₀ are each hydrogen, (o) R₅ is hydrogen, R₆ is chlorine,R₇, R₈ and R₉ are each hydrogen and R₁₀ is ethyl, (p) R₅ is hydrogen, R₆is chlorine, R₇, R₈ and R₉ are each hydrogen and R₁₀ is hydroxyethyl,(q) R₅, R₆, R₇ and R₈ are each hydrogen and R₉ and R₁₀ are eachhydroxyethyl, (r) R₅ is methyl, R₆, R₇ and R₈ are each hydrogen and R₉and R₁₀ are each methyl, (s) R₅ is methyl, R₆, R₇ and R₈ are eachhydrogen, R₉ is ethyl and R₁₀ is carbamylmethyl, (t) R₅ is methyl, R₆,R₇ and R₈ are each hydrogen, R₉ is ethyl and R₁₀ is mesylamino ethyl,and (u) R₅ is hydrogen, R₆ is chlorine, R₇ and R₈ are each hydrogen andR₉ and R₁₀ are each methyl; (2) a dye wherein ##STR25## R₁, R₂, R₃ andR₄ are selected from the following groups of values: (a) R₁ is methyl,R₂ is hydrogen, R₃ is amino and R₄ is hydrogen or methyl, (b) R₁ ismethyl, R₂ is hydrogen, R₃ is acetylamino and R₄ is methyl, (c) R₁ ismethyl, R₂ is hydrogen, R₃ is carbamylamino and R₄ is hydrogen, and (d)R₁ is methoxy, R₂ is hydrogen, R₃ is acetylamino and R₄ is hydrogen; andR₅, R₆, R₇, R₈, R₉ and R₁₀ are selected from the following group ofvalues: (e) R₅ is methyl, R₆ is methoxy, R₇ is hydrogen, R₈ is methyl,R₉ is hydrogen and R₁₀ is hydrogen, and (f) R₅ is hydrogen, R₆ ismethyl, R₇ is hydrogen, R₈ is methyl, R₉ is hydrogen and R₁₀ ishydrogen; (3) a dye wherein A is ##STR26## R₁, R₂, R₃ and R₄ areselected from the following groups of values: (a) R₁ is methyl, R₂ ishydrogen, R₃ is methyl and R₄ is hydrogen, (b) R₁ is methyl, R₂ ishydrogen, R₃ is hydrogen and R₄ is methyl, (c) R₁ is methyl, R₂ ishydrogen, R₃ is amino and R₄ is hydrogen, (d) R₁ is methyl, R₂ ishydrogen, R₃ is amino and R₄ is methyl, (e) R₁ is methyl, R₂ ishydrogen, R₃ is acetylamino and R₄ is methyl, (f) R₁ is methyl, R₂ ishydrogen, R₃ is carbamylamino and R₄ is hydrogen, and (g) R₁ is methoxy,R₂ is hydrogen, R₃ is acetylamino and R₄ is hydrogen; and R₅, R₆, R₇,R₈, R₉ and R₁₀ are selected from the following groups of values: (h) R₅is hydrogen, R₆ is chloro, R₇ is hydrogen, R₈ is hydrogen, R₉ ishydrogen and R₁₀ is methyl, (i) R₅, R₆, R₇, and R₈ are hydrogen, R₉ isethyl and R₁₀ is carbamylmethyl and (j) R₅, R₆, R₇ and R₈ are hydrogen,R₉ is ethyl and R₁₀ is mesylaminoethyl; and (4) a dye wherein A is##STR27## R₁ is methyl, R₂ is hydrogen, R₃ is carbethoxy amino, R₄ ishydrogen, and R₅, R₆, R₇, R₈, R₉ and R₁₀ are selected from the followinggroups of values: (a) R₅, R₆, R₇ and R₈ are each hydrogen and R₉ and R₁₀are each hydroxyethyl, (b) R₅ is methyl, R₆, R₇ and R₈ are each hydrogenand R₉ and R₁₀ are each methyl, (c) R₅ is hydrogen, R₆ is chlorine, R₇and R₈ are each hydrogen and R₉ and R₁₀ are each methyl, (d) R₅ ismethyl, R₆, R₇ and R₈ are each hydrogen, R₉ is ethyl and R₁₀ iscarbamylmethyl, (e) R₅, R₆, R₇ and R₈ are each hydrogen, R₉ is ethyl andR₁₀ is carbamylmethyl, (f) R₅ is methyl, R₆, R₇ and R₈ are eachhydrogen, R₉ is ethyl and R₁₀ is mesylamino ethyl, and (g) R₅, R₆, R₇and R₈ are each hydrogen, R₉ is ethyl and R₁₀ ismesylaminoethyl,comprising dissolving at least one said dye in ananhydrous solvent selected from the group consisting of ethyl alcohol,isopropyl alcohol, tertiary butyl alcohol, monoethyl ether of ethyleneglycol, monomethyl ether of ethylene glycol, monobutyl ether of ethyleneglycol and their mixtures, wherein a solution is formed which contains0.001 to 5 weight percent of said dye, and maintaining said dye in thepresence of said anhydrous solvent during the storage thereof.
 2. Theprocess of claim 1 wherein said dye has the formula as defined in (1).3. The process of claim 1 where in said dye A is ##STR28## and R₁, R₂,R₃ and R₄ are selected from the following groups of values:(a) R₁ ismethyl, R₂ is hydrogen, R₃ is amino and R₄ is hydrogen or methyl, (b) R₁is methyl, R₂ is hydrogen, R₃ is acetylamino and R₄ is methyl, (c) R₁ ismethyl, R₂ is hydrogen, R₃ is carbamylamino and R₄ is hydrogen, and (d)R₁ is methoxy, R₂ is hydrogen, R₃ is acetylamino and R₄ is hydrogen; andR₅, R₆, R₇, R₈, R₉ and R₁₀ are selected from the following group ofvalues: (e) R₅ is methyl, R₆ is methoxy, R₇ is hydrogen, R₈ is methyl,R₉ is hydrogen and R₁₀ is hydrogen, and (f) R₅ is hydrogen, R₆ ismethyl, R₇ is hydrogen, R₈ is methyl, R₉ is hydrogen and R₁₀ ishydrogen.
 4. The process of claim 1 where in said dye A is ##STR29## andR₁, R₂, R₃ and R₄ are selected from the following group of values:(a) R₁is methyl, R₂ is hydrogen, R₃ is methyl and R₄ is hydrogen, (b) R₁ ismethyl, R₂ is hydrogen, R₃ is hydrogen and R₄ is methyl, (c) R₁ ismethyl, R₂ is hydrogen, R₃ is amino and R₄ is hydrogen, (d) R₁ ismethyl, R₂ is hydrogen, R₃ is amino and R₄ is methyl, (e) R₁ is methyl,R₂ is hydrogen, R₃ is acetylamino and R₄ is methyl, (f) R₁ is methyl, R₂is hydrogen, R₃ is carbamylamino and R₄ is hydrogen, and (g) R₁ ismethoxy, R₂ is hydrogen, R₃ is acetylamino and R₄ is hydrogen; and R₅,R₆, R₇, R₈, R₉ and R₁₀ are selected from the following groups of values:(h) R₅ is hydrogen, R₆ is chloro, R₇ is hydrogen, R₈ is hydrogen, R₉ ishydrogen and R₁₀ is methyl, (i) R₅, R₆, R₇ and R₈ are hydrogen, R₉ isethyl and R₁₀ is carbamylmethyl, and (j) R₅, R₆, R₇ and R₈ are hydrogen,R₉ is ethyl and R₁₀ is mesylaminoethyl.
 5. The process of claim 1 wherein said dye A is ##STR30## and R₁ is methyl,R₂ is hydrogen, R₃ iscarbethoxy amino, R₄ is hydrogen, and R₅, R₆, R₇, R₈, R₉ and R₁₀ areselected from the following groups of values: (a) R₅, R₆, R₇ and R₈ areeach hydrogen and R₉ and R₁₀ are each hydroxyethyl, (b) R₅ is methyl,R₆, R₇ and R₈ are each hydrogen and R₉ and R₁₀ are each methyl, (c) R₅is hydrogen, R₆ is chlorine, R₇ and R₈ are each hydrogen and R₉ and R₁₀are each methyl, (d) R₅ is methyl, R₆, R₇ and R₈ are each hydrogen, R₉is ethyl and R₁₀ is carbamylmethyl, (e) R₅, R₆, R₇ and R₈ are eachhydrogen, R₉ is ethyl and R₁₀ is carbamylmethyl, (f) R₅ is methyl, R₆,R₇ and R₈ are each hydrogen, R₉ is ethyl and R₁₀ is mesylamino ethyl,and (g) R₅, R₆, R₇ and R₈ are each hydrogen, R₉ is ethyl and R₁₀ ismesylaminoethyl.
 6. A process for improving the storage stability of adye selected from the group consisting of:N-[(4'-amino-3'-methoxy-2',6'-dimethyl)phenyl]-2, 6-dimethyl-3-acetylamino benzoquinone imine,N-[(4'-β-hydroxyethylamino-3'-chloro)phenyl]-6-methyl-3-ureidobenzoquinone imine, N-[[4'-N,N-(ethyl,carbamylmethyl)amino]phenyl]-6-methyl-3-carbethoxyamino benzoquinoneimine, N-[(4'-methylamino-3'-chloro)phenyl]-6-methyl-3-ureidobenzoquinone imine,N-[(4'-methylamino-3'-chloro)phenyl]-2,6-dimethyl-3-acetylaminobenzoquinone imine,N-[(4'-hydroxy-2'-chloro)phenyl]-2,6-dimethyl-3-acetylamino benzoquinoneimine, N-[(4'-hydroxy-2'-chloro)phenyl]-6-methyl-3-ureido benzoquinoneimine, N-[[4'-N,N-(ethyl,carbamylmethyl)amino-2'-methyl]phenyl]-6-methyl-3-acetylaminobenzoquinone imine, N-[[4'-N,N-(ethyl,carbamylmethyl)amino-2'-methyl]phenyl]-6-methyl-3-ureido benzoquinoneimine, N-[[4'-N,N-(ethyl,carbamylmethyl)amino]phenyl]-2,6-dimethyl-3-acetylamino benzoquinoneimine, N-[(4'-amino-3'-chloro)phenyl]-2,6-dimethyl-3-acetylaminobenzoquinone imine,N-[(4'-amino-3',6'-dimethyl)phenyl]-6-methyl-3-ureido benzoquinoneimine, N-[[4'-N,N-(ethyl, mesylaminoethyl)amino-2'-methyl]phenyl]-3-amino-6-methyl benzoquinone imine,N-[[4'-N,N-(ethyl, mesylaminoethyl)amino]phenyl]-2,6-dimethyl-3-acetylamino benzoquinone imine,N-[(4'-hydroxy)phenyl]-3-acetylamino-6-methyl benzoquinone imine,N-[(4'-amino-3'-chloro)phenyl]-3-acetylamino-6-methoxy benzoquinoneimine, N-[(4'-hydroxy)phenyl]-3-amino-6-methyl benzoquinone imine,N-[[4'-N,N-(ethyl,carbamylmethyl)amino]phenyl]-3-carbethoxyamino-6-methoxy benzoquinoneimine, N-[(4'-hydroxy-2'-chloro)phenyl]-3-ureido-6-methoxy benzoquinoneimine, N-[(4'-hydroxy-2'-chloro)phenyl]-3-acetylamino-6-methoxybenzoquinone imine, N-[[4'-N,N-(ethyl,carbamylmethyl)amino]phenyl]-3-ureido-6-methyl benzoquinone imine,N-[[4'-N,N-(ethyl, carbamylmethyl)amino]phenyl]-3-acetylamino-6-methoxybenzoquinone imine, N-[(4'-hydroxy)phenyl]-3-acetylamino-2,6-dimethylbenzoquinone imine,N-[[4'-N,N-(di-β-hydroxyethyl)amino]phenyl]-3-acetylamino-6-methylbenzoquinone imine,N-[(4'-methylamino-3'-chloro)phenyl]-3-ureido-6-methoxy benzoquinoneimine, and N-[[4'-N,N-(ethyl,carbamylmethyl)amino-3'-methyl]phenyl]-3-carbethoxyamino-6-methoxybenzoquinone imine,comprising dissolving at least one said dye in ananhydrous solvent selected from the group consisting of ethyl alcohol,isopropyl alcohol, tertiary butyl alcohol, monoethyl ether of ethyleneglycol, monomethyl ether of ethylene glycol, monobutyl ether of ethyleneglycol and their mixtures, wherein a solution is formed which contains0.001 to 5 weight percent of said dye, and maintaining said dye in thepresence of said anhydrous solvent during the storage thereof.
 7. Theprocess of claim 1 where said solution contains 0.002 to 1 weightpercent of said dye.
 8. The process of claim 1 wherein said solutionalso contains an azo dye, an anthraquinone dye, a nitrobenzene dye, a1,5-diaminobenzoquinone or an aryl azo pyridine N-oxide.